Organopolysiloxane copolymer useful as surfactant

ABSTRACT

AN ORGANOPOLYSILOXANE COPOLYMER OF THE FORMULA,   R2-(CNH2N-O)X-R3-R2-SI-O-(R2-SI-O)A-(SI(-R)-O-(R&#39;&#39;-   (CNH2N-O)X-R2))B-R2-SI-R3-(CNH2N-O)X-R2   WHEREIN R, R2 ARE LOWER MONOVALENT HYDROCARBON RADICALS, R&#39;&#39; AND R3 ARE LOWER DIVALENT HYDROCARBON RADICALS, A HAS A VALUE OF AT LEAST 4, B HAS A VALUE OF AT LEAST 1, N HAS A VALUE OF FROM 2 TO 4 AND X HAS A VALUE OF AT LEAST 5.

United States Patent 3,790,612 ORGANOPOLYSILOXANE COPOLYMER USEFUL ASSURFACTANT William J. Raleigh, Watervliet, N.Y., assignor to GeneralElectric Company No Drawing. Original application May 27, 1970, Ser. No.41,067, now Patent No. 3,654,195. Divided and this application Oct. 14,1971, Ser. No. 189,446

Int. Cl. C07f 7/08 U.S. Cl. 260-448.2 B Claims ABSTRACT OF THEDISCLOSURE An organopolysiloxane copolymer of the formula,

wherein R, R are lower monovalent hydrocarbon radicals, R and R arelower divalent hydrocarbon radicals, a has a value of at least 4, b hasa value of at least 1, n has a value of from 2 to 4 and x has a value ofat least 5.

This application is a division of copending application Ser. No. 41,067,filed May 27, 1970, now U.S. Pat. 3,654,195.

BACKGROUND OF THE INVENTION The present invention relates toorganopolysiloxane copolymers and is pertinent to organopolysiloxanecopolymers useful as surfactants in the formation of polyurethane foams.

Polyurethane foams are prepared by reacting certain complex polyols withvarious polyisocyanates such as aromatic diisocyanates and aromatictriisocyanates, in the presence of water. The Water reacts with theisocyanate groups, resulting in the release of carbon dioxide, whichacts as a foaming agent for the reaction mixture. Such polyurethanefoams are formed by one of two general processes. In one of theseprocesses, a prepolymer is formed by reacting some of the polyol withthe polyisocyanate which is then further reacted with the remainingpolyol and water in the presence of certain surface active agents toproduce the desired foam. In the other process, the polyol,polyisocyanate and other reactants are added together in a single stepto form the foam. The one step process suffers from a number ofdisadvantages over the two step process in that it is more difficult toobtain uniform cell density and uniform cell size as compared to the twostep process. The reason for this is that most surface active agents aremuch more efficient in the two step process than the one step process.The one step process is desirable in industry in that urethane foams areproduced at a much faster rate. Further, manufacturers of foam prefersurfactants or surface active agents that are soluble in the foamreactants is that a foam with better aesthetic properties is produced.

One object of the present invention is to provide a surface active agentthat acts effectively in both the one step and two step urethane foamingprocesses.

It is another aim to provide a surface active agent that is soluble inthe foam reactants used to produce polyurethane foams.

It is yet another aim to provide a surface active agent that producespolyurethane foam of uniform cell density and cell size.

These and other objects of my invention are more fully described in thefollowing detailed description and in the appended claims.

3,790,612 Patented Feb. 5, 1974 p CC SUMMARY OF THE INVENTION Inaccordance with the present invention a new class of liquidorganopolysiloxane copolymers is provided by the formulas:

wherein R, R are lower monovalent hydrocarbon radicals, R and R arelower divalent hydrocarbon radicals, a has a value of at least 4, b hasa value of at least 1, n has a value of from 2 to 4 and x has a value ofat least 5 and preferably from 5 to or more. The value of a+b preferablyvaries from 5 to 15 if the copolymer is to be soluble in thepolyurethane foam reactants and the sum may vary from 5 to 60 to providea surface active agent having good surfactant properties.

DESCRIPTION OF THE PREFERRED EMBODIMENT The radicals R, R are generallyof not more than 16 carbon atoms and preferably not more than 10.

Among the radicals represented by R, R are mononuclear and binucleararyl, such as phenyl, naphthyl, benzyl, tolyl, xylyl,2,6-di-t-butylphenyl, 4-butylphenyl, 2,4,6-trimethylphenyl, biphenyl andethylphenyl; halogensubstituted mononuclear and binuclear aryl, such as2,6- di-chlorophenyl, 4-bromophenyl, 2,5-di-fluorophenyl, 4,4-dichlorobiphenyl, 2' chloronaphthyl, 2,4,6 trichlorophenyl, and2,5-dibromophenyl; nitro-substituted mononuclear and binuclear aryl,such as 4-nitrophenyl and 2,6- di-nitrophenyl; alkoxy-substit uted monoand binuclear aryl, such as 4-methoxyphenyl, 2,6-dimethoxyphenyl,4-tbutoxyphenyl, Z-ethoxyphenyl, 2-ethoxynaphthyl and2,4,6-trimethoxyphenyl; alkyl such as methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, amyl, hexyl,heptyl, octyl, nonyl, decyl, dodecyl and the various homologs andisomers of alkyl; alkenyl such as vinyl, allyl, n-butenyl-l,n-butenyl-2, n-pentenyl-2, n-hexenyl-2, 2,3-dimethylbutenyl 2,n-heptenyl, n-decenyl, n-dodecenyl and the various homologs and isomersof alkenyl; alkynyl such as propargyl, Z-butynyl and the varioushomologs and isomers of alkynyl; haloalkyl such as chloromethyl,iodomethyl, bromomethyl, fluoromethyl, chloroethyl, iodoethyl,bromoethyl, fiuoroethyl, trichloromethyl, diiodoethyl, tribromomethyl,trifluoromethyl, dichloroethyl, chloro-n-propyl, bromo-n-propyl,iodoisopropyl, bromo-n-butyl, bromo-tertbutyl, 1,3,3-trichlorobutyl,1,3,3-tribromobutyl, chloropentyl, bromopentyl, 2,3-dichloropentyl,3,3-dibromopentyl, chlorohexyl, bromohexyl, 2,4-dichlorohexyl,2,3-dibromohexyl, 1,3,4-trichlorohexyl, chloroheptyl, bromoheptyl,fluoroheptyl, 1,3- dichloroheptyl, 1,4,4-trichloroheptyl,2,4-dichloromethylheptyl, chlorooctyl, bromooctyl, iodooctyl,2,4-dichloromethylhexyl, 2,4-dichlorooctyl, 2,4,4-trichloromethylpentyl,1,3,5-tribromooctyl and the various homologs and isomers of haloalkyl;haloalkenyl such as chlorovinyl, bromovinyl, chloroallyl, bromoallyl,3-chloro-n-butenyl-l, 3-chloro-n-pentenyl-1, 3-fiuoro-n-heptenyl-l,1,3,3-trichloro-n-heptenyl-5, 1,3,5-trichloro-n-octenyl-6,2,3,3-trichloromethylphenyl-4 and the various homologs and isomers ofhaloalkenyl; haloalkynyl such as chloropropargyl, bromop-ropargyl andthe various homologs and isomers of haloalkynyl; nitroalkyl such asnitromethyl, nitroethyl, nitro-n-propyl, nitro-n-butyl, nitropentyl,1,3-dinitroheptyl and the homologs and isomers of nitroalkyl of not morethan about 10 carbon atoms; nitroalkenyl such as nitroallyl,3-nitro-n-butenyl-1, 3-nitro-n-heptenyl-l, and the various homologs andisomers of nitroalkenyl; nitroal-kynyl such as nitropropargyl and thevarious homologs and isomers of nitroalkynyl; alkoxyalkyl andpolyalkoxya'lkyl such as methoxymethyl, ethoxyme-thyl, butoxymethyl,methoxyethyl, e'thoxyethyl, ethoxyethoxyethyl, methoxyethoxymethyl,butoxymethoxyethyl, ethoxybutoxyethyl, methoxypnopyl, but-oxypropyl,methoxybutyl, butoxybutyl, methoxypentyl, butoxypentyl,methoxymethoxypentyl, butoxyhexyl, methoxyheptyl, ethoxyethoxy and thevarious homologs and isomers of alkoxyalkyl and polyalkoxyalkyl;alkoxyalkenyl and polyalkoxykenyl such as ethoxyvinyl, methoxyallyl,butoxyallyl, methoXy-nbutenyl 1, butoxy-n-pentenyl-l,methoxyethoXy-n-heptenyl-l, and the various homologs and isomers ofalko-xyalkenyl and polyalkoxyalkenyl; alkorryalkynyl andpolyalkoxyalkynyl such as methoxypropargyl and the various homologs andisomers of alkoxyalkynyl and polyalkoxyalkynyl; cycloalkyl, cycloalkenyland alkyl, halogen, alkoxy and nitro-substituted cycloalkyl andcycloalkenyl such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, 6-methylcyclohexyl, 2,5-dimethylcycloheptyl,4-butylcyclopentyl, 3,4-dich1orocyclohexyl, 2,6-dibromocycloheptyl,-methoxycyclooctyl, 2-nitrocyclopentyl, lcyclopentenyl,3-methyl-1-cyclopentenyl, S-methoxy-l-cyclopentenyl,3,4-dimethyl-l-cyclopentenyl, 2,5-dimethoxyl-cyclopentenyl,S-methyl-S-cyclopentenyl, 3,4-dichloro- S-cyclopentenyl,S-(tert-butyl)-1-cyclopentenyl, 2-nitro-1- cyclohexenyl, l-cyclohexenyl,3-methyl-1-cyclohexenyl, 3,4-dimethyl-l-cyclohexenyl and6-methoxy-1-cyclohexenyl; and cyanoalkyl such as cyanomethyl,cyanoethyl, cyanobutyl and cyanoisobutyl.

In the same Formula 1, R' and R can be saturated and unsaturateddivalent hydrocarbon radicals such as alkylene, which includesmethylene, ethylene, propylene, butylene, pentylene, hexylene and thevarious homologs and isomers of alkylene; haloalkylene such aschloromethylene, chloroethylene and the various h-omologs and isomers ofhaloal-kylene; mononuclear and binuclear arylene, such as phenylene,naphthylene, benzylene, tolylene; halogen-substituted mononuclear andbinuclear arylene, such as 2,4-dichlorophenylene,4,4-di-chlorobiphenylene, nitro-substituted mononuclear and binucleararylene, such as 4-nitrophenylene and 2,6-di-nitrophenylene;alkoxysubstituted mono and binuclear arylene, such as4-methoxy-phenylene, 2,6-dimethoxyphenylene; alkenylene or substitutedalkylene such as butylenylene; alkynylene such as ethynylene;haloalkenylene such as chloropropylenylene, iodopropylenylene;nitroalkenylene such as nitroethylenylene, nitro-n-propylenylene,nitroPn-butylenylene, nitropentylenyleue; alkoxyalkylene andpolyalkoxyalkylene such as methoxymethylene,ethoxymethylenemethoxyethylene, ethoxyethylene, ethoxyethoxyethylene,butoxmethoxyethylene; alkoxyalkenylene and polyalkoxyalkenylene such asmethoxypropylenylene; cycloalkylene and alkyl, halogen, alkoxy andnitro-substituted cycloalkylene, and cycloalkenylene such ascyclopentylene, cyclohexylene, 6-methylcyclohexylene; cyanoalkylene suchas cyanomethylene, cyanoethylene, cyanobutylene and cyanoisobutylene;carboxy-substituted alkyl or alkylene such as carboxymethyl orcarboxymethylene, carboxyethyl, carboxypropyl, carboxybutyl;oxyalkenylene and oxyalkylene, oxyalkynylene; and carbamyl-substitutedalkyl or alkylene such as carbamylmethyl or carbamylmethylene,carbamylethyl, carbamylpropyl, carbamylbutyl.

The above substituent radicals for R and R may generally have up to 16carbon atoms and preferably up to 10 carbon atoms and include thevarious homologs and isomers of the radicals that have been identifiedabove.

The sum of d-l-b in Formula 1 is preferably to 15 for polymers that aresoluble in urethane foam reactants. However, good surface active agentsare obtained when the sum of a+b varies from 5 to 60.

The organosilane compounds of Formula I can be prepared by the simpleesterification of a liquid car-boxyalkyly and alkylene-containingorganopolysiloxanes having the formula:

with a liquid polyalkylene glycol monomer having the formula:

wherein R and R are alkylene carboxy radicals as previously defined ofpreferably not more than 10 carbon atoms and R, R a, b, n and x are aspreviously defined.

The carboxy-alkyl and alkylene-containing organopolyhydrolysis andcondensation of a diorganodichlorosilane of the formula:

( R SiCl with a cyanoalkyldiorganochlorosilane having the formula:

where R is as previously defined and R is an arylene or alkylene radicalpreferably having not more than 10 carbon atoms as previously definedfor the R, R radicals and such that R CO is equivalent to R During thehydrolysis and condensation of the reactants of Formulas 4 and 5, thevarious silicon-bonded chlorine atoms are replaced by silicon-bondedhydroxyl groups which intercondense to form siloXane linkages and thenitrile radical hydrolyzes to form a carboxyl radical.

The cyanoalkyldiorganochlorosilanes of Formula 5 are prepared byeffecting reaction between a diorganochlorosilane having the formula:

where R is as previously defined and either acrylonitrile,methacrylonitrile or allyl cyanide in the presence of a suitablecatalyst. Illustrative of the diorganosilanes within the range ofFormula 6vare dimethylchlorosilane, methylphenylchlorosilane,diphenylchlorosilane and diphenyl chlorosilane. Products within thescope of Formula 5 which can be prepared by reacting adiorganochlorosilane of Formula 6 with acrylonitrile, methacrylonitrileor allyl cyanide include for example,dimethyl-beta-cyanoethylchlorosilane,methylphenyl-beta-cyanoethylchlorosilane,diphenyl-gamma-cyanopropylchlorosilane, and methylcycloheXyl-beta-cyanopropylchlorosilane. Thecyanoalkyldiorganochlorosilanes of Formula 5 are characterized by thefact that the nitrile group is attached to a carbon atom which is atleast one carbon atom removed from the silicon.

Illustrative of the diorganodichlorosilane within the scope of Formula 4which are hydrolyzed and condensed with thediorganocyanoalkylchlorosilane of Formula 5 are dimethyldichlorosilane,methylphenyldichlorosilane, diphenyldichlorosilane,methylethyldichlorosilane, methylcyclohexyldichlorosilane andmethylvinyldichlorosilane.

The diorganodichlorosilane of Formula 4 is mixed withdiorganocyanoalkylchlorosilane in the proper proportion and the mixtureis added slowly to water with stirring so as to form a uniform mixtureof the organochlorosilanes and water to facilitate the hydrolysis andcondensation of the silicon-bonded chlorine atoms and the hydrolysis ofthe nitrile groups to carboxyl groups. In general the amount of Wateremployed in the hydrolysis and condensation is sufiicient to hydrolyzeall of the silicon-bonded chlorine atoms and sufficient to provide asolvent for the hydrogen chloride which results from the hydrolysis.Preferably, the amount of water is maintained at a low value so as toprovide a concentrated hydrogen chloride solution or even to beinsufficient to dissolve all of the hydrolysis chloride. Where theamount of water is insufiicient to dissolve the hydrogen chloridegenerated, it is desirable to maintain the reaction mixture underpressure, such as a pressure of about 50 pounds per square inch. Theamount of water employed is from about 0.75 to 1.25 parts by weight perpart of the mixture of the organochlorosilanes of Formulas 4 and 5. Thehydrolysis and condensation reaction is exothermic and the temperatureincreases to a maximum of about 70 C. during the course of thehydrolysis and condensation which takes place in about 1 to 6 hours.

After completion of this hydrolysis and condensation reaction, Water andhydrogen chloride are stripped to yield a reaction mixture containing aprecipitate of ammonium chloride from the hydrolysis of the nitrilegroup to the carboxyl group. The precipitate is filtered and thereaction mixture is then dried. In order to insure a uniformcomposition, the dried and filtered hydrolyzate is equilibrated withsulfuric acid. In general, satisfactory results are obtained by addingfrom about 1 to 5 percent by weight of 86% sulfuric acid to thehydrolyzate and heating the reaction mixture at a temperature in therange of 75 C. to 125 C. for about 1 to 3 hours. At the end of this timethe reaction mixture is cooled to room temperature and washed with waterto yield a product of the formula:

(7) R R R HO CR S i [silo] S iR CO H I t 1'1 Ht wherein R and R are asdefined previously.

The compound of Formula 7 is then reacted with the cyclic compound ofthe formula:

and the cyclic compound of the formula: (9) (HO CR RSiO) where R is asdefined previously and R represents alkylene and arylene radicals asdescribed previously with reference to R wherein R CO is equivalent toR.

The compounds of Formulas 8 and 9 are added to the compound of Formula 7in the mole ratio of 1 mole of Formula 8 to 1 mole of Formula 9 to 4moles of Formula 7 to provide the polymer of Formula 2. The compound ofFormula 2 is obtained by equilibrating in sulfuric acid the compounds ofFormulas 8 and 9 with the polymer of Formula 7. Generally 0.1 to 0.5part of sulfuric acid is added per part of the polymer. In the resultingreaction mixture the bonds of cyclic compounds of Formulas 8 and 9 are'broken. The addition reaction of these compounds to the polymer ofFormula 7 is exothermic. However, additional heat is added to thereaction mixture to maintain the reaction mixture at a temperaturegenerally in the range of 80l50 C. and preferably at 100l20 C. Duringthe reaction the mixture is thoroughly agitated with a stirrer and thereaction is allowed to proceed for 1-6 hours and preferably 2-4 hours atthe above temperature. When the reaction is completed the reactionmixture is neutralized with NaHCO Water is then added so as to form anorganic phase and an aqueous phase. The organic phase is then separatedfrom the water phase and water is once more added to the organic phaseto Wash it free of impurities soluble in the aqueous phase. The waterphase is then separated from the organic phase to leave the organicphase free of water soluble imprities. Any other remaining impuritiesare then separated out by filtering the organic phase to obtain a pureproduct of Formula 2.

The organopolysiloxane copolymer of Formula 1 is then formed by theesterification of the organopolysiloxane of Formula 1 with thepolyethylene glycol monoether of Formula 3.

The polyethylene glycol monoethers are formed by reacting a monohydricalcohol of the formula R"OH with an alkylene oxide or a mixture ofalkylene oxides. By controlling the reaction conditions during thereaction between the aforementioned monohydric alcohol and the alkyleneoxide, the molecular weight of the polyalkylene glycol monoethers can becontrolled. While any polyalkylene glycol monoether within the scope ofFormula 3 can be used in the practice of the present invention, it ispreferred that the material contain at least 5 oxyalkylene units andpreferably that x in Formula 3 vary from 5 to 100. In order to be mosteffective in the preparation of polyurethane foams, it is preferred thatthe polyethylene glycol monoether have a molecular weight of from about300 to 5,000.

The polyalkylene glycol monoethers employed in the practice of thepresent invention contain oxyalkylene groups of from 2 to 4 carbonatoms. Included within these oxyalkylene groups are oxyethylene,oxypropylene-1,2, oxypropylene-1,3, oxybutylene-1,2, etc. The monoethersof Formula 3 can contain a number of oxyalkylene groups which areidentical to each other or the oxyalkylene groups can comprise a mixtureof various types of oxyalkylene groups. In the preferred embodiment ofthe invention, the oxyalkylene groups are oxyethylene. Many of thesepolyethylene glycol monoethers employed in the practice of the presentinvention are described in US. Pats. 2,425,755 and 2,448,644.

In preparing the organopolysiloxane copolymers of Formula 1, anyconventional means of esterification can be used. Preferably threemolecules of the polyalkylene glycol monoether of Formula 3 is reactedwith one molecule of the organopolysiloxane of Formula 2 to produce thecopolymer of Formula 1. By controlling the particularcarboxyalkyl-containing organopolysiloxane of Formula 2 and theparticular polyalkylene glycol monoether of Formula 3, the relativeproportions of the silicon portion and polyoxyalkylene portion of thecopolymer of Formula 1 are controlled. Preferably the silicone portionof the copolymer comprises 78-82 mole percent of the total molecularweight of the copolymer. The proportion of the silicone portion of themolecule to the polyalkylene glycol monoether portion is quite importantin producing a good surface active agent. It Was found that when thecopolymers have the above stated mole percent of this silicone portionof the molecule an efficient surface active agent is obtained.

In one acceptable method of forming the copolymers of Formula 1, theorganopolysiloxane of Formula 2 and the polyalkylene glycol monoether ofFormula 3 are mixed together in the presence of a suitable inert solventand a catalyst and heated at the refiux temperature of the catalystuntil esterification is effected. Suitable solvents include thehydrocarbon solvents such as benzene, toluene, xylene, and mineralspirits. The amount of solvent employed is not critical and may varyWithin Wide limits. Satisfactory results have been obtained by usingfrom about 0.5 to 5 parts of solvent per part of the mixture of thepolysiloxane of Formula 2 and the monoether of Formula 3. One extremelyuseful catalyst for the esterification reaction is p-toluene sulfonicacid. The amount of catalyst being employed is not critical, withsatisfactory results being obtained using from 0.1 to 5 percent byweight of the catalyst based on the weight of the reaction mixture. Thereaction usually takes about 2 to 24 hours before esterification iscompleted. After esterification is completed, the catalyst isneutralized with sodium bicarbonate and the solution is then filtered toremove impurities. The solvent is distilled from the reaction mixture toleave a copolymer within the scope of Formula 1 which is a clear, lowviscosity fluid.

In another method for form-ing the compound of Forrnula 1, thepolyethylene glycol monoether of Formula 3 1s reacted in the presence ofa catalyst and in a solvent with a compound of the formulas:

( R'TNCO RIOH wherein R is an unsaturated single hydrocarbon radical.The radical R may be selected from alkenyl; alkynyl; halogen-substitutedalkenyl, and alkynyls; nitroalkenyl; mtroalkynyl; alkoxyalkenyl andpolyalkoxyalkenyl; alkoxyalkynyl and polyalkoxyalkynyl; and cycloalkenyland alkyl, halogen, alkoxy and nitro-substituted cycloalkenyl. Theradicals which R represents generally have not more than 16 carbon atomsand preferably not more than 10 carbon atoms.

The compounds of Formulas 10 and 11 are reacted with the monoethers ofFormula 3 in a solvent such as benzene, toluene, etc. The amount ofsolvent is not critical and is preferably 0.5 to 4 parts of the reactionmixture. In order for the reaction to proceed efiiciently there is alsopresent a catalyst which is an acid catalyst such as paratoluenesulfonic acid when the compound of Formula 11 is reacted and a tincatalyst such as tin octoate when the compound of Formula 10 is reacted.The tin octoate catalyst is utilized in 0.001 to 0.l part of catalystper part of the reaction mixture. The acid catalyst is utilized in 0.01to 1 part of acid per part of the reaction mixture. The reaction isgenerally carried out in a temperature range of 50 to 150 C. andpreferably at a temperature range of 90 to 100 C. in 1 to 3 hours. Afterthe reaction has proceeded to completion the catalyst is filtered out ofthe reaction mixture and the solvent is distilled off to produce aproduct having the formula:

wherein R and R are as defined previously.

The products of Formulas 12 and 13 are then reacted with a polysiloxaneof the formula:

(14) HR SiO (R SiO). (RHSiO) R SiI-I in an addition reaction to form thecopolymer of Formula 1. The polysiloxane of Formula 14 is formed byreacting amixture of cyclic organosiloxanes of the formula:

and a cyclic hydroorganosiloxane of the formula:

( 16) (RHSiO v with a diorganodisiloxane of the formula:

( 17 RgSiOSiRz wherein R is as previously defined and w and v are 3 or4.

The compounds of Formulas 13, 16 and 17 are mixed in a molar proportionof 9 moles of the compound of Formula 15 with 1 mole of the compound ofFormula 16 with 1 mole of compound of Formula 17 to react to produce apolymer of Formula 14. These compounds are equilibrated in the presenceof an acid catalyst such as H 80 Thus, preferably 1-5 parts by weight H80 is added per part by weight of the reaction mixtures. Although thereaction mixture may be heated to 60-80 C. to allow the equilibrationreaction to proceed at a rapid rate, the reaction may also take place atroom temperature. The reaction mixture is constantly agitated with amechanical agitator and the reaction is allowed to proceed for 10-20hours. When the reaction has reached completion the acid in the reactionmixture is neutralized with NaHCO The resulting neutralized reactionmixture is washed with water and the organo phase is separated out fromthe water phase. Any remaining impurities in the organo phase are thenfiltered out to yield a pure product of the Formula 14.

The polymer of Formula 14 is then reacted in an SiI-I olefinic additionreaction with the unsaturated alkenyl carboxyl alkylene glycol monoetherof Formula 12 or with the alkenyl oxyalkylene glycol of Formula 13 toproduce the product of Formula 1. In one suitable method the reactantsare mixed together in the presence of a suitable solvent and a catalystand heated at an elevated temperature until the addition reaction iscompleted. Suitable inert solvents that may be used are hydrocarbonsolvents such as benzene, toluene, xylene, and mineral spirits. Almost0.5 to 5 parts of solvent are used per part of the compounds taking partin the addition reaction. Suitable catalysts for the addition reactionare generally metal organic compounds such as tin hexoate andparticularly tin octoate. The amount of the catalyst employed is notcritical with satisfactory results being obtained with 0.1 to 10 percentby weight of the catalyst based on the weight of the reaction mixture.The reaction is continued until the SiH addition is completed whichusually takes from about 1 to 12 hours. After the addition reaction iscompleted the catalyst is separated out by filtration and the solvent isdistilled from the reaction mixture to leave a copolymer within thescope of Formula 1 which is a clear, low viscosity fluid. In forming theproduct of Formula 1 three moles of the compounds of Formulas 12 or 13are reacted with one mole of the polymer of Formula 14.

In using the organopolysiloxanes of the present invention as additivesin the production of polyurethane foams, the organopolysiloxane ofFormula 1 is added to the other ingredients of the polyurethane foamreaction mix ture in proportions as described below. The polyurethanefoam reaction mixture comprises three essential ingredients, namely, apolyisocyanate, a polyol and water.

The polyisocyanates which are useful in the practice of the presentinvention are those well known polyisocyanates which are conventionallyused in the manufacture of polyurethane foams. Generally speaking, thesepolyisocyanates contain at least 2 isocyanate groups per molecule, whichare separated from each other by at least 3 carbon atoms, i.e.,isocyanate groups are not on adjacent carbon atoms in the formulation.These polyisocyanates may be aromatic or aliphatic and can becharacterized by the formula:

where V represents a polyvalent organic radical having a valence c andwhere c has a value of at least 2, and preferably from 2 to 3,inclusive. The number of isocyanate groups is, of course, equal to thenumber of free valences in the radical V. In general, the radical Vconsists preferably of carbon and hydrogen atoms only, but may alsoinclude oxygen atoms. Preferably, also, the radical y is a mononucleararomatic radical. Illustrative of the various polyisocyanates which canbe employed in the practice of the present invention can be mentioned,for example, 2,4-toluene diisocyanate; m-phenylene diisocyanate;methylene-bis (4 phenylisocyanate); 4- mcthoxy-m-phenylene diisocyanate;1,6-hexamethylene diisocyanate; 2,4,6-toluene triisocyanate;2,4,4'-diphenylether triisocyanate; 2,6-toluene diisocyanate;3,3'-bitolylene-4,4-diisocyanate; diphenylmethane-4,4'-diisocyanate;3,3'-dimethyldiphenylmethane 4,4 diisocyanate; triphenylmethanetriisocyanate; dianisidine diisocyanate, etc. In addition to using onlya single isocyanate in the production of polyurethane foams, it is alsocontemplated that mixtures of various isocyanates can be employed. Infact, the preferred isocyanate material employed in the practice of thepresent invention is a mixture of by weight of 2,4-toluene diisocyanateand 20% by weight of 2,6-toluene diisocyanate.

The polyols employed in the practice of the present invention are thosepolyols conventionally used in the manufacture of polyurethane foamproducts. Chemically,

these materials fall into one of two general categories.

The first is the hydroxy-containing polyester and the second is thehydroxy-containing polyether. The polyesters are conventionally formedby the reaction of a polyhydric alcohol with a dibasic acid. Thepolyhydrio alcohol is employed in excess so that the resulting materialcontains free hydroxyl groups. Illustrative of the types of polyesterpolyol materials employed in the production of polyurethane foams arepolyesters formed by the reaction between dibasics acids, such as adipicacid, with polyhydric alcohols such as ethylene glycol, glycerine,pentaerythritol, sorbitol and the like. In general, these polyesterpolyols are prepared so as to contain from 2 to about 6 hydroxyl groupsper molecule.

The polyether polyols employed in the practice of the present inventionfor the manufacture of urethane foams can be subdivided into two types,the first of which is a polyalkylene glycol such as polyethylene glycolor polypropylene glycol or mixed polyethylenepolypropylene glycol. Thesecond type is a polyoxyalkylene derivative of a polyhydric alcohol suchas polyoxyalkylene derivatives of glycerine, a trimethylolethane, atrimethylolpropane, neopentyl glycol, sorbitol, etc. These materials arewell known in the art and are prepared by eifecting reaction between analkylene oxide or a mixture of alkylene oxides and the polyhydricalcohol. One common type of material is prepared by reacting1,2-propylene oxide with glycerine to form a triol containing 3polyoxypropylene groups attached to the glycerine nucleus.

These polyester polyols and polyether polyols are characterized bymolecular weights of the order of from about 350 up to 10,000 or more.The particular type of triol and its molecular weight are generallydetermined by the characteristics of the urethane foam and the economicsinvolved. In general, either the polyester polyols or the polyetherpolyols can be used interchangeably in the manufacture of either rigidpolyurethane foams, semi-rigid polyurethane foams or flexiblepolyurethane foams. The distinguishing characteristic of the materialswhich control the type of foam in which they are to be used is themolecular weight. In general, the polyol used in the formation of rigidfoams has a molecular weight in the range of from about 350' to 600.Generally,these polyols are triols or higher polyols. For themanufacture of semi-rigid foams, the polyol has a molecular weight inthe range of from about 600 to 2500 and is generally a triol. For themanufacture of flexible foams, the polyol has a molecular weight of therange from about 2500 up to about 10,000 and is a triol or a mixture ofa triol and a diol.

While the polyisocyanate and the polyol are the essential ingredients inthe polyurethane foam reaction mixture, these reaction mixtures oftencontain a number of other ingredients in minor proportions. One of themost common of these other ingredients is water. Water reacts with theisocyanate groups and results in the liberation of carbon dioxide whichserves as a blowing agent. However, it is often impossible to form lowdensity foams using the carbon dioxide generated in situ as the onlyblowing agent, since the generation of carbon dioxide also results incross-linking of the foam. Sometimes excessive cross-linking will occurif sufficient Water is added to the reaction mixture to generate thedesired amount of carbon dioxide. Other times, because of the particularpolyol and isocyanate employed in the reaction mixture, it is notdesirable to employ any water, since any water induced generation ofcross-linking will result in a foam which is too brittle.

Accordingly, in those cases where it is not desirable to add any water,or in those cases where it is not feasible to add the amount of waterdesired, the reaction mixture often includes a separate blowing agent,such as a low boiling inert liquid. The ideal liquid is one which has aboiling point slightly above room temperature, i.e., a temperature ofabout 20 to 25 C., so that the heat generated by the exothermic reactionbetween the hydroxyl groups and the isocyanate groups will warm thereaction mixture to a temperature above the boiling point of the liquidblowing agent and cause it to boil. Suitable blowing agents includealkanes having appropriate boiling points, but the most desirableblowing agent has been found to be trichlorofiuoromethane, which iscommercially available under the trade name Freon 11.

Other ingredients often found in polyurethane foam reaction mixtures arevarious catalysts. For example, it is often desirable to add a catalystto facilitate the reaction between water present in the reaction mixtureand isocyanate groups. A typical type of catalyst for this reaction is atertiary amine catalyst. These amine catalysts are Well known in theart, and include materials such as N methylmorpholine,dimethylethanolamine, triethylamine, N,N'-diethylcyclohexylamine,dimethylhexadecylamine, dimethyloctadecylamine, dimethylcocoamine,dimethylsilylamine, N-cocomorpholine, triethylene diamine, etc.

To catalyze the reaction between the hydroxyl groups of the polyol andthe isocyanate, polyurethane foam reaction mixtures often contain acatalyst comprising a metal salt of an organic carboxylic acid. Mostoften this curing agent is a tin salt such as tin stearate, dibutyl tindilurate, tin oleate, tin octoate, etc.

The properties of the various components of the polyurethane foamreaction mixtures may vary within Wide limits as is well known in theart. When water is added to the reaction mixture, it is present in anamount sufiicient to generate the amount of carbon dioxide desired.Generally, when water is employed it is present in an amount up to about5 parts per parts, by weight, of the polyol. The polyisocyanate isgenerally present in an exess ever the amount theoretically required toreact with both the hydroxyl groups of the polyol and any Water presentin the reaction mixture. Generally, the polyisocyanate is present in anexcess equal to about 1 to 15 percent, by weight. When a tertiary aminecatalyst is present in the reaction mixture, it is generally employed inan amount equal to from about 0.001 to 3.0 parts' per 100 parts, byweight, of the polyol. When a metal salt curing agent is present, it isgenerally employed in an amount equal to from about 0.1 to 1.0 per 100parts, by weight, of the polyol. When a separate blowing agent isemployed, it is generally employed in an amount equal to from about 5 to25 parts per 100 parts, by weight, of the polyol.

When employing the organopolysiloxane copolymer of Formula 1 as an aidin the formation of polyurethane foams, the copolymer is generallypresent in an amount equal to from about 0.25 to 7.5 parts by Weightbased on 100 parts by Weight of the polyol in the reaction mixture.

Polyurethane foams can be prepared by one of two general methodsemploying the organopolysiloxane copolymer of Formula 1. In the first,and preferred process, all of the reactants are rapidly mixed togetherand the reaction mixture is allowed to foam. After foaming has beencompleted, the resulting form can be cured, if desired, by heating atelevated temperatures, e.g., a temperature of from about 75 to C. forserval hours. Alternatively, the foam may be stored at room temperatureuntil complete cure has been effected in times of from 24 hours to 48hours or more.

In one modification of the second process, a prepolymer is formed fromthe polyol and the polyisocyanate to give a prepolymer containing excesspolyisocyanate. This prepolymer is then mixed with the other reactantssuch as water, tertiary amine catalyst, blowing agent, curing catalystand polysiloxane copolymer and allowed to foam.

In another modification of the second process, the polyisocyanate and aportion of the polyol are reacted together to form a base resin. Whenfoaming is desired, the remainder of the polyol as Well as the otheringredients of the reaction mixture are added to the base resin and themixture is stirred and allowed to foam. Again, curing can be effected atroom temperature or at an elevated temperature.

Regardless of the foaming process in which the organopolysiloxanecopolymer of Formula 1 is employed, and regardless of whether thecomponents of the reaction mixture are such as to produce rigid foams,semi-rigid foams or flexible foams, the use of these organopolysiloxanecopolymers results in foams having smaller and more uniform cell sizesthan corresponding foams prepared from prior art materials.

Because of the complexity of the well known technology surrounding themanufacture of polyurethane foams of all types, no attempt will be madehere to discuss the many variations in technique and formulations whichcan be employed. For further details on the technology of polyurethanefoams, reference is made to the voluminous patent and technicalliterature on the subject, including Pat. 2,901,445Harris;Polyurethanes, Bernard A. Dornbrow, Reinhold Publishing Corporation, NewYork (1957); Polyurethanes, a Versatile Synthetic for a Dynamic Area,Polyurethane Associates ((1956); Urethane Applications LaboratoryMemorandum No. 60, Apr. 28, 1961 by Wyandotte Chemicals Corporation,Research Division; Polyurethane Foam Catalysts, Technical Bulletin No.B6-R4, June 1960, Armour Industrial Chemical Company; Dabco, DataBulletin No. 4, July 20, 1959, Houdry Process Corporation.

The following examples are illustrative of the practice of the inventionand are not intended for purpose of limitation. All parts are by weight.The primary allyl car bamate of the polyether alcohol of the exampleswas prepared by reacting allylisocyanate with a polyether alcohol in thepresence of a tin octoate catalyst and 0.5 part of toluene solvent perpart of the reaction mixture. After the reaction had proceeded for 2hours at a temperature of 95 C., the catalyst was filtered off and thesolvent was distilled oil to yield the polyether alcohol product.

EXAMPLE 1 Using a 5 liter three-necked flask to contain the reactionmixture, there was introduced into the flask 2,694 parts of a compoundof the formula 222 parts of octamethylcyclotetrasiloxane and 396 partsof carboxyethylmethylcyclotetrasiloxane. The flask had an agitator,thermometer and condenser for refluxing the reaction mixture. To thereaction mixture there was added a catalyst of 99.0 parts of 86% H 80and the entire mixture was heated at 100 C. After the reaction hadproceeded for three hours the temperature was lowered and NaHCO wasadded to the mixture to neutralize the acid. The organic phase wasseparated from the aqueous phase, washed with water and then separatedagain from the aqueous phase. The organic phase was then filtered toremove impurities and yield a product of the formula:

Some of the properties of this compound are:

Viscosity at 77 F. 175 Weak acid number 153 CIH: H0 0 (CHz)|SiO CH: K m2H ctsk remaining organic phase was filtered to yield a product withinFormula 1 having the structure:

0 SIiO (CH1); ii-O(CHCH:O)12CH5 CH:

EXAMPLE 2 There was introduced into a 2 liter three-necked flask 666parts of octanethylcyclotetrasiloxane, 60 parts ofmethylhydrogencylcotetrasiloxane and 134 parts of tetramethyldisiloxane.The reaction mixture was then equilibrated by adding to it 26 parts of86% by weight H The flask was fitted with an agitator, thermometer andcondenser so that the reaction mixture would be constantly agitated andrefluxed. The reactants were constantly agitated at a tem perature of 25C. for 15 hours. After this time period had passed the acid in thereaction mixture was neutralized with NaI-ICO and the aqueous phase thatformed was separated from the organic phase. The organic phase waswashed with Water and again the aqueous phase was separated from theorganic phase. The organic phase was then filtered to remove anyremaining impurities to produce a product having the formula:

siH

This compound had the following properties:

Viscosity at 77 F. ctsk 5.9 Percent H (by weight) 0.34

One mole of the above compound was then mixed with 3 moles of a primaryallyl carbamate of a polyether alcohol in the presence of the solvent,toluene, where there was present 0.5 part of solvent per part of thereactants. There was also present 0.0001 part of complexed platinumwhich acted as the catalyst in the addition reaction. After the reactionhad proceeded at a temperature of C. for 4 hours the temperature waslowered and the solvent was distilled off. There was then left a productwithin the scope of Formula 1 having the formula:

1. An organopolysiloxane copolymer having the formulas:

where R and R are lower monovalent hydrocarbon radicals of not more than10 carbon atoms, R and R are divalent hydrocarbon radicals selected fromthe class consisting of alkylene mononuclear arylene, alkylene-carboxyand alkylene carbamyl of up to 10 carbon atoms, a has a value of atleast 4, b has a value of at least 1, n has a value of from 2 to 4 and xhas a value of at least 5.

2. The copolymer of claim 1 wherein a has a value of 9, b has a value of1 and R, R are methyl.

3. The copolymer of claim 1 having the formula:

CH3 TSIJO [(CH2)2C 0 (0 112110); CH3]](CHa)2Si =0 ()(0 n 2u)X 3 4. Thecopolymer of claim 1 having the formula:

5. A process for forming an organopolysiloxane copolymer having theformulas:

14 wherein R and R are lower monovalent hydrocarbon radicals of not morethan 10 carbon atoms, R and R are alkylenecarboxy radicals of up to 10carbon atoms, a has a value of at least 4, b has a value of at least 1,n has a value of from 2 to 4, and x has a value of at last 5, byreacting a siloxane polymer of the formula:

3,398,104 8/1968 Haluska 260-4488 R X 2,846,458 8/1958 Haluska 260-448.8R X 3,280,160 10/1966 Bailey 260448.8 R X DANIEL E. WYMAN, PrimaryExaminer P. F. SHAVER, Assistant Examiner US. Cl. X.R.

25 2602.5 AM, 260448.2 E

